DK154254B - FUNGICID PREPARATION CONSISTS OF A MIXTURE OF PROCHLORAZ AND A TRIAZOLIC COMPOUND AND USES THEREOF - Google Patents

Description

DK 154254 B

The present invention relates to a composition having useful fungicidal properties as well as uses thereof.

Prochloraz is a known fungicide and is the commonly recognized name for 1- [N-propyl-N-2- (2,4,6-trichlorophenoxy) -ethylcarbamoyl] -imidazole. Salts and complexes of this compound with metal salts are also known to have fungicidal activity.

It has now been found that mixtures of prochloraz or salts or complexes thereof with metal salts and some triazole fungicides lead to improvement in the fungicidal action.

Therefore, a fungicidal composition of the present invention contains prochloraz or a salt or complex thereof with metal salts and one of the triazole fungicides triadimefon, propiconazole and dichlobutrazole. The triazole fungicides can usually also form salts and complexes with metal salts, and these fall within the scope of the invention.

Triadimefon is the recognized common name for 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone. It is a commercially available fungicide described in British Patent Specification 1,364,619. Propiconazole (formerly called proconazole) is 1- [2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-yl-methyl] -1,2,4-25 triazole (British Patent 1,522. 657). Dichlobutrazole is 1- (2,4-dichlorophenyl) -4,4-dimethyl-2- (1,2,4-triazol-1-yl) -pentan-3-ol (Belgian Pat. No. 857,836).

The fungicidal properties of the latter two compounds are described in the 1979 British Crop Protection 30 Conference reports on pages 565 and 508, respectively, and in the aforementioned patents.

The amount ratio of prochloraz to its derivatives, on the one hand, and the triazole fungicide, on the other hand, may vary within wide limits, but is generally within the range of 400: 1 to 1: 400, preferably 10: 1 to 1:10, especially 5: 1 to 1: 5 and especially 4: 1 to 1: 4. These proportions are based on the weight of the 2

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free bases.

In addition, other pesticides may be used in conjunction with the active ingredients described above, provided that they do not adversely affect the interaction of the fungicidal components. For example, it is sometimes useful to include additional fungicides that expand the field of activity to combat a larger fungal spectrum.

The compositions of the invention are particularly useful for the control of mildew (Erysiphe graminis) on cereal crops such as wheat, barley, oats and rye and other leaf diseases such as avniplet (Septoria nodorum), ray spot (Rhynchosporium secalis), eye patch (Pseudocercosporella herrtle rust fungi (e.g. Puccinia graminis). Certain 15 compositions of the present invention can be used to control seed-borne organisms such as stink fire (Tilletia caries) on wheat, naked oat fire and naked barley fire (Ustilago nuda and Ustilago hordei) on barley and oats, oats and oats and stubble (Pyrenophora avenae) -20. Sickness (Pyrenophora graminis) on barley. The preparations can also be used on rice to control the side sickness of the rice (Pyricularia oryzae), on garden crops such as apple trees for the control of stain basket (Venturia inaequalis), roses for the control of mildew (Sphaerotheca pannosa), cucumbers for the control of Botea 25 of Sclerotinia homeocarpa; moreover, some of the preparations can be used on stored products to control the occurrence of storage organisms found on citrus fruits, potatoes, sugar beets, apples, pears, etc. (eg Penicillium spp, Aspergillus spp 30 and Botrytis cinerea).

Metal complexes of prochloraz are described in British Patent Specification 1,567,521, and a particularly preferred complex is that formed with manganese chloride and wherein the molar ratio of prochloraz to manganese is 4: 1. The fungicidal compositions 35 of the invention can be used in many forms and are often most conveniently prepared in aqueous form immediately prior to use. A process for making such a 3

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preparation is known under the term "tank mix" in which the fungicidal active ingredients in their commercially available form are mixed by the farmer in a suitable amount of water for direct use.

In addition to the tank mixture immediately prior to use, the compositions containing prochloraz and the triazole fungicide can be worked up into a more concentrated primary preparation diluted with water or other diluent prior to use to provide a composition which can be applied to the crop 10 by spraying. Such compositions may contain a surfactant in addition to the active ingredients, and typical examples thereof are a dispersion in an aqueous or non-aqueous carrier, an emulsifiable concentrate, a dispersible powder or a powder. In a concentrated primary composition, the concentration of active ingredients may vary within wide limits and may be, for example, 5 to 95% by weight of the composition. The primary composition is diluted to produce compositions for application to a growing crop where the amount of active ingredient supplied to the crop is as set forth below.

An emulsifiable concentrate, also known as "miscible liquid", contains a solution of the active ingredients in a non-aqueous solution and together with one or more emulsifiers. An emulsion is formed when the emulsifiable concentrate is mixed with water.

A dispersible powder contains the active ingredients in finely divided form together with one or more dispersants, so that a stable aqueous dispersion of the active ingredients is formed by mixing the powder with water.

Generally, a finely divided, inert solid diluent such as kaolin or diatomaceous earth (sold under the trademark "Celite" ®) is generally incorporated into the dispersible powder.

A powder contains the active ingredients intimately mixed with a solid powdery diluent such as kaolin.

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The concentration of the active ingredients (when used as the only active components) in a composition for direct application to a crop by conventional methods is preferably in the range of 0.001 to 5% by weight of the composition, in particular 0.005 to 5% by weight, but more concentrated preparations containing up to 40% may be desirable in the case of atomizing spray preparations.

The fungicidal compositions described can be applied directly at the time of sowing so that the active composition combats the growth of fungi that attack the seeds. A suitable feed rate is in the range of 0.025 to 10 kg / hectare, preferably in the range of 0.04 to 5.0 kg / hectare.

A composition according to the invention can also be applied directly to the plants, for example by spraying or powdering, either at the time the fungus has begun to appear on the plant or before the emergence of the fungus as a preventive measure. In either case, the preferred application is spraying the leaves. It is generally important to achieve good fungal control at the early stages of plant growth, as this is the time when the plant can be severely damaged. For cereal crops such as wheat, barley and oats, it is often desirable to spray the plant at or before growth stage 6 (Feeke's scale), although an additional 25 treatments when the plant is more mature can improve resistance to the growth or spread of fungi. It can also sometimes be useful to treat a plant's roots before and during planting, for example by dipping the roots into a suitable liquid or solid preparation. When the composition of the invention is applied directly to the plants, an appropriate feed rate is 0.05 to 5 kg / hectare, preferably 0.25 to 1.5 kg / hectare.

According to the invention, the fungicidal composition can be particularly conveniently used for application to seeds to combat seed-borne fungal infestation, especially on cereals. This method is particularly useful for treating grain seed against attacks of, for example, leaf spot disease on oats, strip disease on barley, 5

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naked barley grit, naked oat fire and stink fire on wheat.

If seed grains are to be stored in a storage room or container, it may be convenient to treat the storage room or container with a composition of the invention in place of or in addition to the processing of the grains themselves. A suitable amount of application for seed dressings is 0.02 to 1.0 g per gram. kg, e.g. 0.05 g to 0.25 g per kg. kg.

Furthermore, according to the invention, the fungicidal composition can be used with great advantage in general to fight leaf diseases on cereal crops, for example wheat, barley, oats or rye, ie fungal attack on leaves of cereals.

Hereby, the composition is preferably applied by spraying the leaves on the grain in growth.

Fungicide compositions of the invention will be elucidated in the following by some examples describing in vitro experiments with mixtures of prochloraz and the triazole fungicides, where synergistic action was found.

Example 1

Aqueous suspensions of prochloraz and a commercially available triadimephone-containing preparation were prepared and these suspensions were incorporated into a molten malt extract agar in such quantities as to obtain the desired concentration of the active ingredients in the agar. The molten agar was then poured into 9 cm petri dishes and allowed to solidify. The agar in each dish was seeded with a plug taken from an agar culture of Botrytis cinerea, and the dishes 3Q were incubated at 20 ° C for 3 days. The diameters of the colonies were then measured and the amount of growth calculated as a percentage of the growth observed with a control. Each of the experiments was repeated four times and an average value of the observed growth as a percentage of control is shown in Table 1.

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Table 1

Concentration Concentration Found Expected by prochloraz of triadimefon growth as growth as% (ppm) (ppm)% of control of control __ growth__ growth (E ·,) 5 0.125 0 43 0 50 29.4 0 25 64 0 12.5 83, 4 0.125 50 0 12.6 10 0.125 25 0 27.5 0.125 12.5 0 35.9

To show the existence of synergism between the 15 active components, the results were treated in the manner described by S. R. Colby (1967, Calculating Synergistic and Antagonistic Responses of Herbicide Combinations. Weeds Γ5, 20-22). The calculated values of E ^, the expected growth expressed as% of the weight of the control, 20 X1Y1 were calculated from the equation where is the growth as% of the control of prochloraz at a given concentration by use alone, 25 and is the growth as% of the control of triadimefon at a given concentration by use alone. If the growth observed is less than E ^, the results show synergism. In the above table, the results with the mixture show signs of synergism.

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Example 2

Aqueous suspensions of technical grade prochloraz and triadimefone were prepared and used in agar plate experiments in a similar manner to that described in Example 1 except that a culture of Alternaria solani is used.

The results obtained are shown in Table II below.

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Table II

"1" “........ ...................... --i i

Concentration Concentration j Found Expected by prochloraz of triadimefon growth as% growth as% (ppm) (ppm) of control of control growth growth, () 0.125 65 0.25 51 0.5 24 12.5 94 10 25 90 50 75 100 54 0.125 12.5 36 61 0.125 25 31 58.5 15 0.125 50 25 48.75 0.125 100 20 35.1 0.25 12.5 31 47.9 0.25 25 24 45.9 0.25 50 26 38.3 20 0.25 100 23 27.5 0.5 12.5 21 22.6! 0.5! 25 15 21.6 0.5 I 50 13 18.0 0.5 '100 i 12 13.0 __i_i ----- 25

Example 3

An experiment was conducted in a similar manner to that described in Example 2, with the exception that a culture of Fusarium oxysporum fsp cucumerinum was used.

When triadimefone was used alone in an amount of 0.5 ppm, there was no reduction in organism growth, whereas by combining this amount of triadimefon with prochloraz in the amounts shown in Table III, growth was observed less than that observed. with prochloraz alone.

Table III

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Concentration of Concentration Estimated growth prochloraz of triadimefon as% of control (ppm) (ppm) growth 1 0 34 5 0.5 0 41 0.25 0 51 0.125 0 65 1 0.5 29 0.5 0.5 36 10 0.25 0.5 49 0.125 0.5 47 _

Example 4

Solutions of prochloraz and triadimefon in acetone were added to portions of Ustilago hordei 15 stock suspensions to give the desired concentrations of the fungicides. The solutions were shaken for 48 hours and then the solid was separated by filtration and the amount of organism that had grown was determined by weighing. Five parallel experiments were performed and the average weights of the organism after 20 drying expressed as% of control are shown in Table IV below. The "expected growth" shown in the fourth column of the table was calculated by the method outlined above by Colby.

_Table IV__ 25 Concentration Concentration Estimated Expected Growth | of prochloraz of triadimephone growth as% as% of control-j (ppm) (ppm) of control-growth (E ^) j ___ growth ________ 1 1.25 0 95.6 2.50 0 78.9 30 5.00 0 42.7 0 7.5 74.6 1.25 7.5 27.3 71.3 2.5 7.5 26.2 41.1 5.0 7.5 13.6 31.9

Example 5 9

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Samples of a suspension of Ustilago hordei were shaken with acetone and solutions of prochloraz and triadimefon in which the fungicides had the concentrations as shown in Table 5 V. After 48 hours, samples were removed and microscopically determined by means of a hemacytometer. of cells present. The results in Table V show that mixtures containing 100 ppm fungicide overall reduced the number of cells to lower level 10 than 100 ppm of each of the two fungicides by use alone.

Table V

Concentration Concentration Number of cells taken by prochloraz of triadimefon taken, expressed as 15 (ppm) (ppm)% of control 100 72.7 100 75.6 75 25 68.7 50 50 58.5 20 25 75 53.7

Example 6

Example 1 was repeated, replacing triadimefon with diclobutrazole and using as a culture Pyricularia oryzae. Synergism was demonstrated as shown in Table VI.

Table VI

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Concentration Concentration Detected Expected growth of prochloraz of diclobutrazole growth as% as% of control (ppm) (ppm) of control growth (E-) growth 5 0.03 0 87 0.06 0 81 0 0.015 93 0 0, 03 96 0 0.06 99 10 0.03 0.015 80 81 0.03 0.03 79 84 0.03 0.06 67 86 0.06 0.015 72 75 0.06 0.03 64 78 15 0.06 0, 06 52 80

Example 7

Example 2 was repeated, but triadimefon was replaced with propiconazole. Synergism was demonstrated as shown in Table VII

Table VII

- i

Concentration Concentration Detected Expected growth of prochloraz of propiconazole growth as% as% of control (ppm) (ppm) of control growth (E · ^) ___ growth ___ 0.12 0 91 25 0 0.03 100 0 0.06 100 0 0.12 98 0.12 0.03 84 91

0.12 0.06 84 91 I

0.12 0.12 79 89

Claims (5)

A fungicidal composition, characterized in that it contains prochloraz (1- [N-propyl-N-2- (2,4,6-trichlorophenoxy) -ethylcarbamoyl] -imidazole) or a salt thereof or a complex thereof with a metal salt , as well as one of the triazole fungicides triadimefone (1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone), propiconazole ( 1- [2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-yl-methyl] -1,2,4-triazole) (Dichlorophenyl) -4,4-dimethyl-2- (1,2,4-triazol-1-yl) -pentan-3-ol). A fungicidal composition according to claim 1, characterized in that the triazole fungicide is a triadimefone or a salt thereof or a complex thereof with a metal salt. A fungicidal composition according to claim 1, characterized in that the triazole fungicide is propiconazole or a salt thereof or a complex thereof with a metal salt. Use of the fungicidal composition as claimed in claim 1 for application to seeds for the control of seed-borne fungal infestations, especially on cereals. Use of the fungicidal composition of claim 1 for controlling fungal attack on leaves of 25 grains. 30 35